CN112851582B - Piezochromic material, encryptable material prepared from piezochromic material and decryption method - Google Patents

Piezochromic material, encryptable material prepared from piezochromic material and decryption method Download PDF

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CN112851582B
CN112851582B CN202110018418.5A CN202110018418A CN112851582B CN 112851582 B CN112851582 B CN 112851582B CN 202110018418 A CN202110018418 A CN 202110018418A CN 112851582 B CN112851582 B CN 112851582B
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piezochromic
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CN112851582A (en
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雷云祥
张心宇
黄小波
吴华悦
刘妙昌
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Wenzhou University
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Abstract

The invention relates to the technical field of piezochromic materials, in particular to a piezochromic material, an encryptable material prepared from the piezochromic material and a decryption method. The invention provides a plurality of piezochromic materials, specifically researches the characteristics of the piezochromic materials, combines the piezochromic materials according to different reaction behaviors of the piezochromic materials under external stimulation, and can be used for encrypting important image or text information.

Description

Piezochromic material, encryptable material prepared from piezochromic material and decryption method
Technical Field
The invention relates to the technical field of piezochromic materials, in particular to a piezochromic material, an encryptable material prepared from the piezochromic material and a decryption method.
Background
The piezochromic material is an intelligent material which responds to force stimulation, and changes the physical accumulation mode of molecules under the force stimulation to change the luminous color or luminous intensity of the molecules and the like. The method has wide application prospect in the fields of pressure sensors, information storage, trademark anti-counterfeiting, luminescent devices and the like.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
A first object of the present invention is to provide a piezochromic material.
A second object of the invention is to provide a cipherable material made with piezochromic material.
A third object of the present invention is to provide an encryption/decryption method for the encryptable material.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a piezochromic material comprising any one of the following structures:
Figure BDA0002887827620000011
R1any one selected from H and phenyl; r2Selected from phenyl,
Figure BDA0002887827620000012
Any one of (1), R3Selected from any one of phenyl, 4-methylphenyl and anthryl.
In a specific embodiment of the present invention, the piezochromic material comprises any one of compound a, compound B and compound C:
Figure BDA0002887827620000021
the invention also provides application of the piezochromic material in preparation of encryptable materials.
The invention also provides a cipherable material comprising at least one of the piezochromic materials described above.
In a specific embodiment of the present invention, the encryptable material includes at least one of the compound a and the compound B, and the compound C.
In a specific embodiment of the present invention, the encryptable material further comprises a substrate, and the piezochromic material is disposed on a surface of the substrate. Further, the piezochromic material is arranged on the surface of the substrate in a solid form.
The invention also provides a decryption method of the encryptable material, which comprises the following steps:
recording an initial fluorescence image of the encryptable material;
carrying out pressure treatment on the encryptable material, carrying out organic steam fumigation treatment on the encryptable material subjected to pressure treatment, and recording a fluorescence image subjected to fumigation treatment;
and comparing the initial fluorescence image with the fluorescence image after fumigation treatment.
In a specific embodiment of the invention, the organic vapor comprises ethanol vapor.
In a specific embodiment of the present invention, the method of pressure-induced treatment comprises: and grinding the piezochromic material.
In one embodiment of the invention, the fluorescence image is recorded under illumination of 300-400 nm.
The invention also provides an organic monomolecular white light emitting material which has the following structure:
Figure BDA0002887827620000031
in a specific embodiment of the present invention, the organic monomolecular white light emitting material has a chromaticity coordinate of (0.34 ).
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a plurality of piezochromic materials, specifically researches the characteristics of the piezochromic materials, combines the piezochromic materials according to different reaction behaviors of the piezochromic materials under external stimulation, and can be used for encrypting important image or text information.
(2) The invention also provides an organic monomolecular white light emitting material which can obtain different fluorescence emission by changing the concentration of a compound, the monomolecular white light emitting material successfully realizes the white light emission, and the CIE (CIE) calculation coordinates are (0.34 ).
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a normalized fluorescence emission spectrum of Compound A provided in the examples of the present invention under different conditions; inset is fluorescence image of compound a under different conditions;
FIG. 2 is a normalized fluorescence emission spectrum of compound B provided in the examples of the present invention under different conditions; the inset is a fluorescence image of compound B under different conditions;
FIG. 3 is a normalized fluorescence emission spectrum of Compound C provided in the examples of the present invention under different conditions; inset is fluorescence image of compound C under different conditions;
FIG. 4 is a normalized UV absorption spectrum of Compound A provided in the examples of the present invention under different conditions;
FIG. 5 is a normalized UV absorption spectrum of compound B provided in the examples of the present invention under different conditions;
FIG. 6 shows normalized UV absorption spectra of Compound C provided in the examples of the present invention under different conditions;
FIG. 7 shows fluorescence images of the encrypted materials prepared from compound A, compound B and compound C in different states; wherein (a) is an initial fluorescence image; (b) is a fluorescence image after the pressure-induced treatment; (c) the fluorescence image after fumigation treatment is obtained;
FIG. 8 shows fluorescence spectra of Compound C in THF solvent at different concentrations;
FIG. 9 is a CIE coordinate and fluorescence image of Compound C provided in the examples of the present invention in THF solvent at concentrations of 2. mu. mol/L, 8. mu. mol/L, and 20. mu. mol/L.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
A piezochromic material comprising any one of the following structures:
Figure BDA0002887827620000051
R1any one selected from H and phenyl; r2Selected from phenyl,
Figure BDA0002887827620000052
Any one of (1), R3Selected from any one of phenyl, 4-methylphenyl and anthryl.
In a specific embodiment of the present invention, the piezochromic material comprises any one of compound a, compound B and compound C:
Figure BDA0002887827620000053
Figure BDA0002887827620000061
the invention also provides application of the piezochromic material in preparation of encryptable materials.
The invention also provides a cipherable material comprising at least one of the piezochromic materials described above.
In a specific embodiment of the present invention, the encryptable material includes at least one of the compound a and the compound B, and the compound C.
In a specific embodiment of the present invention, the encryptable material further comprises a substrate, and the piezochromic material is disposed on a surface of the substrate. Further, the piezochromic material is arranged on the surface of the substrate in a solid form.
The invention also provides a decryption method of the encryptable material, which comprises the following steps:
recording an initial fluorescence image of the encryptable material;
carrying out pressure treatment on the encryptable material, carrying out organic steam fumigation treatment on the encryptable material subjected to pressure treatment, and recording a fluorescence image subjected to fumigation treatment;
and comparing the initial fluorescence image with the fluorescence image after fumigation treatment.
In a specific embodiment of the invention, the organic vapor comprises ethanol vapor.
In a specific embodiment of the present invention, the method of pressure-induced treatment comprises: and grinding the piezochromic material.
In one embodiment of the invention, the fluorescence image is recorded under illumination of 300-400 nm.
The invention also provides an organic monomolecular white light emitting material which has the following structure:
Figure BDA0002887827620000071
in a specific embodiment of the present invention, the organic monomolecular white light emitting material has a chromaticity coordinate of (0.34 ).
The compound 9a, the compound 1a and the compound 1b of the present invention can be prepared by referring to the methods described in the prior art, and the specific synthetic routes can be respectively as follows:
the general synthesis of compound 9a is as follows:
compound D2A mixture of (1.0mmol), aldehyde (1.5mmol), piperidine (0.4mL) and acetonitrile (10mL) was stirred in N2The reaction was refluxed for 10h under an atmosphere. The reacted mixture was poured into 50mL of methanol and cooled to room temperature to precipitate the crude product. And washing the crude product with methanol for three times, and drying to obtain a corresponding pure compound.
Figure BDA0002887827620000072
Compound 9 a: yellow solid (248mg, 74% yield).1H NMR(DMSO-d6,400MHz):δ8.13-8.12(m,1H),7.70-7.59(m,6H),7.39(d,J＝16.0Hz,1H),7.28(d,J＝8.0Hz,2H),7.15(d,J＝2.0Hz,1H),6.98(d,J＝1.6Hz,1H),2.35(s,3H)ppm.HRMS(ESI)m/z:[M+H]+calculated for C23H17N2O,337.1341；found,337.1344.
The general synthesis of compounds 1a and 1b is as follows:
compound D1A mixture of (1.0mmol), aldehyde (6.0mmol), piperidine (1.0mL) and acetonitrile (10mL) was stirred in N2The reaction was refluxed for 24h under an atmosphere. The reacted mixture was poured into 50mL of methanol and cooled to room temperature to precipitate the crude product. And washing the crude product with acetone and methanol for three times respectively, and then drying to obtain a corresponding pure compound.
Figure BDA0002887827620000081
When compound 1a is synthesized, the aldehyde in the starting material has the formula:
Figure BDA0002887827620000082
when compound 1b was synthesized, the aldehyde in the starting material was of the formula:
Figure BDA0002887827620000083
example 1
This example provides compound a and a method for its preparation, the synthetic route is as follows:
Figure BDA0002887827620000084
the specific synthesis steps comprise:
taking 0.3mmol of compound 9a, 1.2mmol of piperidine and KH2PO40.9mmol of the total solution of the organic acid, and adding2.5mL of DMSO at 120 ℃ and N2Stirring and reacting for 14h under the atmosphere; after the reaction, after the reaction solution was cooled to room temperature, 20mL of CH was added2Cl2Water and CH2Cl2Extracting for three times, collecting organic phase, drying with anhydrous sodium sulfate, removing organic solvent by rotary evaporation under reduced pressure, and purifying by column chromatography (eluent 5: 1 petroleum ether and ethyl acetate) to obtain white solid 116.2mg, which is compound A, with a yield of 72%.
Characterization data for compound a are as follows:
1H NMR(DMSO-d6,500MHz):δ7.33-7.28(m,3H),7.22-7.20(m,2H),7.01(d,J＝8.0Hz,2H),6.83(d,J＝8.5Hz,2H),5.62(s,1H),4.16(d,J＝5.0Hz,1H),3.45-3.43(m,4H),3.28-3.23(m,2H),3.22-3.17(m,2H),2.85-2.75(m,2H),2.21(s,3H),1.64-1.60(m,6H),1.55-1.51(m,2H),1.44-1.35(m,4H)ppm.13C NMR(CDCl3,125MHz):δ161.8,156.2,153.7,152.1,140.7,140.3,135.7,129.0,128.7,127.9,127.7,127.4,118.9,115.6,93.9,87.8,50.2,47.6,38.3,33.7,26.0,25.2,24.8,24.4,21.0ppm.HRMS(ESI)m/z:[M+H]+calculated for C33H37N4,489.3018；found,489.3004.
example 2
This example provides compound B and a method for its preparation, the synthetic route being as follows:
Figure BDA0002887827620000091
the specific synthesis steps comprise:
taking 0.3mmol of compound 1a, 1.2mmol of 4-phenylpiperidine and KH2PO40.9mmol, added to 2.5mL of DMSO at 120 ℃ and N2Stirring and reacting for 14h under the atmosphere; after the reaction, after the reaction solution was cooled to room temperature, 20mL of CH was added2Cl2Water and CH2Cl2Extracting for three times, collecting organic phase, drying with anhydrous sodium sulfate, removing organic solvent by rotary evaporation under reduced pressure, and performing column chromatography (eluent at volume ratio of 5: 1)Petroleum ether and ethyl acetate) to obtain 184.0mg of an orange solid, i.e., compound B, with a yield of 94%.
Characterization data for compound B are as follows:
1H NMR(DMSO-d6,400MHz):δ7.70(d,J＝15.2Hz,1H),7.55(d,J＝7.6Hz,2H),7.37-7.24(m,13H),7.21-7.17(m,4H),7.12(d,J＝7.6Hz,2H),5.72(s,1H),4.83-4.81(m,1H),4.26(d,J＝10.4Hz,2H),3.97-3.85(m,2H),3.07-2.92(m,2H),2.96-2.88(m,4H),2.81-2.72(m,2H),1.94-1.91(m,2H),1.86-1.70(m,4H),1.48-1.32(m,2H)ppm.13C NMR(CDCl3,125MHz):δ161.4,153.0,151.8,150.7,146.2,145.1,143.0,136.9,135.4,128.62,128.57,128.5,128.4,128.3,127.4,127.3,126.9,126.74,126.71,126.4,126.2,123.6,118.9,116.6,94.3,87.9,50.1,49.9,47.6,47.4,43.1,42.6,37.9,33.48,33.47,33.43,32.9,32.3ppm.HRMS(ESI)m/z:[M+H]+calculated for C46H45N4,653.3639；found,653.3645.
example 3
This example provides compound C and a method for its preparation, the synthetic route being as follows:
Figure BDA0002887827620000101
the specific synthesis steps comprise:
taking 0.3mmol of compound 1b, 1.2mmol of piperidine and KH2PO40.9mmol, added to 2.5mL of DMSO at 120 ℃ and N2Stirring and reacting for 14h under the atmosphere; after the reaction, after the reaction solution was cooled to room temperature, 20mL of CH was added2Cl2Water and CH2Cl2Extracting for three times, collecting organic phase, drying with anhydrous sodium sulfate, removing organic solvent by rotary evaporation under reduced pressure, and purifying by column chromatography (eluent is petroleum ether and ethyl acetate at volume ratio of 5: 1) to obtain orange solid 105.1mg, which is compound C, with yield of 50%.
Characterization data for compound C are as follows:
1H NMR(DMSO-d6,500MHz):δ8.51(t,J＝3.5Hz,1H),8.32(s,1H),8.25(d,J＝15.5Hz,1H),8.14(d,J＝8.5Hz,1H),8.06(d,J＝9.5Hz,1H),7.90-7.86(m,3H),7.45(t,J＝7.0Hz,1H),7.40-7.36(m,3H),7.27(t,J＝7.0Hz,1H),7.21(t,J＝8.0Hz,1H),7.19-7.14(m,4H),6.26(d,J＝15.5Hz,1H),6.07(t,J＝10.0Hz,1H),5.91(s,1H),3.57-3.55(m,4H),3.27-3.19(m,5H),2.81(q,J＝9.0Hz,1H),1.74-1.66(m,4H),1.63-1.60(m,2H),1.53-1.41(m,6H)ppm.13C NMR(CDCl3,125MHz):δ161.0,153.5,151.8,150.4,137.8,132.7,132.4,131.9,131.6,131.2,130.9,129.7,129.6,129.0,128.9,128.7,128.1,127.7,126.9,126.3,126.2,125.5,125.3,125.2,124.72,124.67,124.5,122.1,119.3,118.2,93.3,87.7,50.2,47.4,34.7,33.9,26.0,25.3,24.9,24.2ppm.HRMS(ESI)m/z:[M+H]+calculated for C50H45N4701.3639; found,701.3631 Experimental example 1
FIGS. 1 to 3 show normalized fluorescence emission spectra of compound A, compound B and compound C under different conditions; the insets are fluorescence images of the corresponding compounds under different conditions, respectively. As can be seen, when the original sample of Compound A was ground in a mortar with a pestle, the fluorescence changed from blue to cyan, with an emission wavelength from 441nm to 471nm, red-shifted by 30 nm. The fluorescence quantum efficiency is reduced from 18% to 8%, and the red-shifted piezochromic property is shown. However, the orange light-emitting compound B and red light-emitting compound C were ground to convert into green light emission and orange light emission, respectively, that is, the emission spectra of compound B and compound C showed blue shifts of 17nm and 15nm, respectively. The results show that compound B and compound C exhibit blue-shifted fluorescence enhanced piezochromic properties.
The absorption spectra of the three compounds before and after grinding and after fumigation or after recrystallization are shown in fig. 4 to 6, respectively. The absorption spectrum of the original sample of compound a after grinding showed a significant red shift. The results show that the milling treatment results in a flattening of the molecular conformation and an enhancement of the molecular conjugation, resulting in a red-shift of the fluorescence emission and a reduction of the fluorescence quantum efficiency. Although the formation of an excimer based on a pi-pi interaction can also lead to a red shift of the fluorescence spectrum, according to previous reports the maximum absorption wavelength before and after milling should remain unchanged, which is not in line with the results of compound a. Unlike compound a, the absorption spectra of the milled samples of compound B and compound C showed a significant blue shift compared to the original samples. These results indicate that the milling process results in a more distorted molecular conformation, reducing the molecular conjugation, resulting in a blue-shifted emission and an increase in fluorescence intensity. When ground samples of compound a and compound B were fumigated with ethanol vapor, their emission spectra were nearly identical to the original samples, so the fumigated samples could be restored to their corresponding original samples, indicating the reversibility of their piezochromic properties. However, for compound C, the sample after pressing was restored to the original sample only by recrystallization, and the conventional organic vapor fumigation treatment could not be used.
The fluorescence properties and fluorescence quantum yields of compound a, compound B and compound C in the different states are shown in table 1.
TABLE 1 fluorescence Properties and fluorescence Quantum yields of the Compounds in the different states
Figure BDA0002887827620000121
Experimental example 2
Since compound a, compound B and compound C exhibit different response behaviors to external stimuli, they can be applied in combination to encryption of important image or text information. First, hollowed animal and plant patterns were placed on paper, and then solid samples of compound a, compound B and compound C were attached to the hollow patterns of grass, fawn and mushroom, respectively, with commercial solid glue, as shown in fig. 7 (a). When the orange grass, blue deer and red mushroom patterns were ground with a metal spatula, their colors were changed to cyan, green and orange, respectively, under 365nm irradiation, as shown in fig. 7 (b). When the image is further fumigated with ethanol vapor, the fluorescence color of grass and fawn is restored to the original state, but the amorphous compound C of mushroom is not converted into a crystalline sample during the fumigation process, so that the encrypted information can be preserved, as shown in fig. 7 (C).
Experimental example 3
Fluorescence spectra of Compound C in THF solvent (10 concentration)-5mol/L) two emission peaks centered at 403nm and 570nm respectively appear, and the solution shows complex fluorescence. And the emission band centered at 570nm has a large peak width, which is advantageous for forming a broadband emission covering the visible range. Therefore, the possibility of compound C emitting white fluorescence in solution was investigated by adjusting the emission intensity of these two peaks. FIG. 8 shows fluorescence spectra of compound C at different concentrations (2-20. mu. mol/L) in THF solvent, with an excitation wavelength of 350 nm. The peak intensity at 570nm varied more than the peak intensity at 403nm with increasing concentration, which resulted in a change in the ratio of the fluorescence intensities of the two peaks. The results show that at concentrations of 2. mu. mol/L, 8. mu. mol/L and 20. mu. mol/L, the solution exhibits pink, white and yellow fluorescence, as shown in FIG. 9. The results show that different fluorescence emissions can be obtained by varying the concentration of compound C and that white light emission is successfully achieved with a single molecule with CIE calculated coordinates (0.34 ).
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (11)

1. Piezochromic materials characterized by comprising any of the following structures:
Figure FDA0003369753070000011
R1any one selected from H and phenyl; r2Selected from phenyl,
Figure FDA0003369753070000012
Any one of (1), R3Selected from any one of phenyl, 4-methylphenyl and anthryl.
2. The piezochromic material according to claim 1, wherein the piezochromic material comprises any one of compound a, compound B and compound C:
Figure FDA0003369753070000013
3. use of the piezochromic material of claim 1 or 2 for the preparation of a cipherable material.
4. A cipherable material comprising compound C and at least one of compound a and compound B according to claim 2.
5. The encryptable material of claim 4, further comprising a substrate, the piezochromic material being disposed on a surface of the substrate.
6. The encryptable material of claim 5, wherein the piezochromic material is disposed on the substrate surface in solid form.
7. Method for decrypting an encryptable material according to any one of claims 4 to 6, characterized in that it comprises the following steps:
recording an initial fluorescence image of the encryptable material;
carrying out pressure treatment on the encryptable material, carrying out organic steam fumigation treatment on the encryptable material subjected to pressure treatment, and recording a fluorescence image subjected to fumigation treatment;
and comparing the initial fluorescence image with the fluorescence image after fumigation treatment.
8. The decryption method of claim 7, wherein the organic vapor comprises ethanol vapor.
9. The decryption method according to claim 7, wherein the method of pressure-induced processing includes: and grinding the piezochromic material.
10. An organic monomolecular white light emitting material characterized by having the following structure:
Figure FDA0003369753070000021
11. the organic single-molecule white light emitting material of claim 10, wherein the chromaticity coordinates of the organic single-molecule white light emitting material are (0.34 ).
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108003859A (en) * 2017-12-19 2018-05-08 南京工业大学 Piezochromic fluorescent molecule and preparation method and application thereof
CN109337670A (en) * 2018-10-09 2019-02-15 大连理工大学 A kind of steam color-changing materials with information encrypt-decrypt function, preparation method and applications
CN111499573A (en) * 2020-05-09 2020-08-07 浙江工业大学 Pressure-induced color-changing fluorescent molecule and preparation method thereof
CN112552226A (en) * 2020-12-10 2021-03-26 青海大学 Force-induced fluorescent color-changing compound, preparation method and application thereof, ink-free rewritable safety paper and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108003859A (en) * 2017-12-19 2018-05-08 南京工业大学 Piezochromic fluorescent molecule and preparation method and application thereof
CN109337670A (en) * 2018-10-09 2019-02-15 大连理工大学 A kind of steam color-changing materials with information encrypt-decrypt function, preparation method and applications
CN111499573A (en) * 2020-05-09 2020-08-07 浙江工业大学 Pressure-induced color-changing fluorescent molecule and preparation method thereof
CN112552226A (en) * 2020-12-10 2021-03-26 青海大学 Force-induced fluorescent color-changing compound, preparation method and application thereof, ink-free rewritable safety paper and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
3,6-Diamino-7,8-dihydroisoquinoline-4-carbonitrile derivatives: unexpected facile synthesis, full-color-tunable solid-state emissions and mechanofluorochromic activities;Xinyu Zhang,等;《Org. Chem. Front.》;20210111;第8卷(第5期);856-867 *

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